Cellulose Derivatives in Food Applications Dow Wolff Cellulosics

Cellulose Derivatives in Food Applications Dow Wolff Cellulosics Vicki Deyarmond vldeyarmond@dow.com March 2012 3/12/2012 1

Agenda Introduction to Cellulose Food Approved Cellulose Derivatives o Key Properties o Functions o Common Applications Most Widely Used Cellulose Ethers in Food Industry o o o Methylcellulose (MC) Hydroxypropyl Methylcellose (HPMC) Sodium Carboxymethylcellulose (CMC) Q&A 3/12/2012 2

What is Cellulose? Worlds most abundant naturally occurring organic substance Cellulose comes from plants, trees and vegetable matter As such, it has always been part of the human diet and a source of dietary fiber In its natural state, cellulose is not soluble in water (chains of cellulose are very tightly bound to each other by H-bonding) 3/12/2012

Cellulose Ethers Water Insoluble Water Soluble 4

Cellulose Derivatives for Food First cellulosics research work begun in 1920 s in Germany Applications in foods (USA) starting in late 1940 s. High purity ( 95% water-soluble dietary fiber) Non-digestible Non-fermentable - no gas o Related to form of 1,4-β-glycosidic bonds between glucose units Non-allergenic GRAS status 3/12/2012 5

Types of Cellulose Derivatives for Food Physically Modified Cellulose Microcrystalline Cellulose (MCC) Cellulose Ethers Hydroxypropylcellulose (HPC) Ethylmethylcellulose (MEC) Ethylcellulose (EC) Methylcellulose (MC) Hydroxypropyl Methylcellulose (HPMC) Sodium Carboxymethylcellulose (CMC) 3/12/2012 7

Microcrystalline Cellulose (MCC) Properties Thixotropic Shear Thinning Reversible Heat Stable Nonionic Powdered & Dispersible Grades Functions/Applications pacifying Agent Foam Stabilizer Anti-caking agent Emulsifier Freeze Thaw Stability Cheese (powdered,shredded) Beverages, Confections, Salad Dressings, Sauces, Whipped Toppings *Labeled as Microcrystalline Cellulose or Cellulose Gel 3/12/2012 8

Hydroxypropyl Cellulose (HPC) Properties Nonionic Surface Active Insoluble in Hot Water >40 C Soluble in rganic Solvents Thermoplastic Functions/Applications Foam Stabilizer Film Former (Flexible) Whipped Toppings, Edible Coatings, Confection Glazes, Extruded Foods *Labeled as Hydroxypropyl Cellulose or Modified Cellulose 3/12/2012 9

Ethylmethyl Cellulose (MEC) Properties Nonionic ph Stable Precipitates From Solution Above 60C (reversible upon cooling) Not widely used Functions/Applications Thickening Agent Filler Anti-Clumping Agent Emulsifier Non Dairy Creams, Low Calorie Ice Creams, Whipped Toppings, Mousse *Labeled as Ethylmethylcellulose, methylethylcellulose or Modified Cellulose 3/12/2012 10

Ethylcellulose (EC) Properties Nonionic Hydrophobic Soluble in rganic Solvents Thermoplastic Functions/Applications Film Former Flavor Fixative Limited Food Approval Flavor Encapsulation, Moisture Barrier Films, Fruit/Vegetable Inks *Labeled as Ethylcellulose 3/12/2012 11

Methylcellulose & Hydroxypropyl Methylcellulose (MC & HPMC) Properties Reversible Thermal Gelation Cold Water Soluble ph Stable Wide Viscosity Range Functions/Applications Binding Boilout Control Film Former Freeze Thaw Stability Formed Foods, Fillings, Sauces, Whipped Toppings, Gluten Free Baked Goods *Labeled as Methylcellulose, Hydroxypropyl Methylcellulose, Modified Cellulose 3/12/2012 12

Sodium Carboxymethylcellulose (CMC) Properties Anionic ph Sensitive Interacts with Proteins High Water Holding Capacity Functions/Applications Freeze Thaw Stability Protein Protection Thickener Texture Control Frozen Foods, Baked Goods, Tortillas, Soups, Sauces, Beverages *Labeled as Sodium Carboxymethylcellulose or Cellulose Gum 3/12/2012 13

Agenda Introduction to Cellulose Food Approved Cellulose Derivatives o Structure Function Relationships o Common Applications Most Widely Used Cellulose Derivatives in Food Industry o o o Methylcellulose (MC) Hydroxypropyl Methylcellose (HPMC) Sodium Carboxymethylcellulose (CMC) Q&A 3/12/2012 14

Methylcellulose (MC) Hydroxypropyl Methylcellulose (HPMC) 3/12/2012 15

MC & HPMC Common Applications Bakery, Gluten Free Fillings Sauces Formed/Extruded Foods Salad Dressings/Marinades Whipped toppings Batters/Coatings Meat/fish preparations Beverage Emulsions 3/12/2012 16

MC & HPMC Advantages Broad viscosity range from very low to extremely high o 19 250,000 cps (2 %, Brookfield) Always available in high quality (not dependant on harvesting) High degree of purity (> 99.5 %) Conformity of all standards for food and pharmaceutical applications Narrow specifications for all relevant product parameters Prepared from wood pulp GM free 17

MC & HPMC - Key Properties/Functions Reversible Thermal Gelation (varying gel strengths) Wide Viscosity Range Thickening Moisture Control (Cold Water Binding) Emulsification, Encapsulation & Film Formation Binding Air Entrainment & Foam Stability Freeze Thaw Stability Provides Soluble Fiber 3/12/2012 18

MC & HPMC Chemistry o Methylcellulose (MC) o Hydroxypropyl methylcellulose (HPMC) Based on the substituent group Methyl Group Methyl Group Hydroxypropyl Group Methylcellulose (MC) Hydroxypropyl methylcellulose (HPMC) 19

MC & HPMC - The Chemistry CH 3 H H H H H CH 2 CH 3 H H H H H CH 2 H H H CH 3 H H H H CH 2 H 3 C H H MC H CH 3 CH 3 CH 3 H H H CH 3 H H H CH 2 CH 2 CHCH 3 H H H H H CH 2 H H H H CH 2 H CH 3 CHCH 2 CH 3 CH 3 H H H HPMC H 3/12/2012 20

Chemistry- Functionality Different chemistries have differences in physical properties Dissolution temperature Gelation Temperature Gel Strength Surface Activity Differences are caused by: The substituent group (Ratio of methyl/hydroxpropyl groups) Relative numbers of the groups (Degree of Substitution: DS) Average chain length of the product (Molecular Weight) 21

MC & HPMC - Different Viscosities Thick ~ 50,000 mpa.s Thin Medium ~ 50 mpa.s ~ 4000 mpa.s 3/12/2012 22

Viscosity Range Viscosity, mpa.s 100,000 10,000 1,000 2 3 1 4 1) 100,000 5 2) 40,000 6 3) 15,000 4) 4,000 7 5) 1,500 8 9 6) 400 7) 100 8) 50 9) 15 10) 5 100 10 10 1 0 1 2 3 4 5 6 7 Wt% gum A rough rule -- For every 1% increase in concentration you will see a 8x increase in viscosity 23

MC & HPMC Effect of Concentration Viscosity build is not linear Effect of ph Viscosity is stable between ph = 3 and 11 Effect of Temperature MUST reach set hydration temperatures to become fully functional. Effect of Salt and Sugar: May delay hydration and hinder viscosity development May precipitate MC & HPMC out of solution if too much salt or sugar May lower gelation temperature 3/12/2012

MC & HPMC Effect of Temperature Hydration Range Gelation Range Gel Strength High Gel MC <50 F 100-114 F (10 C) (38-44 C) Very Firm Conv. MC <55 F 122-131 F (13 C) (38-44 C) Firm HPMC < 77 F - 85 F 143-194 F (25 C - 30 C) (62 C - 90 C) Semi-Firm - Soft 3/12/2012 25

MC & HPMC REVERSIBLE THERMAL GELATIN 3/12/2012 26

MC & HPMC Reversible Thermal Gelation. Heating Cooling 2% MC & HPMC Solutions Gels obtained by heating 2% MC and HPMC Solutions 3/12/2012

MC & HPMC Thermal Gelation Benefits Controls moisture movement Retains shape at high temperatures (Boil out control) Reduces oil uptake Improves coating adhesion (along with film formation) Works alone (no other additives necessary) 3/12/2012 28

MC & HPMC - Thermal Gelation - Binding/Shape Retention 3/12/2012 29

MC & HPMC Thermal Gelation Boil ut Control HPMC (0.5%) Control *Note: maximum sugar content must be less than 50%. 3/12/2012 30

MC & HPMC Thermal Gelation Boil ut Control 0.4% MC vs- 0.15% Xanthan, 0.15% Guar, and starch control 3/12/2012 Before Baking 31

MC & HPMC Thermal Gelation Boil ut Control After Baking 3/12/2012 32

MC & HPMC Thermal Gelation Fat Reduction In French Fry Coatings: Most important property is gel strength gel maintains its integrity during frying o MC has the highest gel strength of the chemistries o Least surface active MC will also gel at the lowest temperature o Ensures film is formed prior to fat being absorbed 3/12/2012 33

% fat MC & HPMC Thermal Gelation Fat Reduction Fat Uptake Reduction With Increasing Methylcellulose Solution Strength 9 8 7 6 5 4 3 2 1 0 0 1 2 3 4 5 6 % low viscosity MC 3/12/2012 34

% Total Fat MC & HPMC - Thermal Gelation Fat Reduction Fat Reduction in French Fry Batters Achieves ~30% reduction in fat 14.00 Developmental Lab Samp Will enable a Reduced Fat claim in retail markets 12.00 10.00 8.00 Note that the batter alone does provide some barrier function~11% 6.00 Control Non- Battered Control Battered Methocel 2% MC A-15 (2%) La Samp (1% 3/12/2012 35

MC & HPMC Thermal Gelation Fat Reduction Cinnamon Buns 3/12/2012 36

MC & HPMC Thermal Gelation Fat Reduction Methylcellulose be used to improve the juiciness and mouthfeel of an already lean beef patty (without adding extra fat) Formulation o o o o 88.4% Lean beef (90% fat free) 10.0% Cold water (<40F) 1.2% Methylcellulose 0.4% Salt Total fat: 10% fat (from meat) (11.3g fat per ¼ lb patty) Store bought patty = 20% (22.6g fat per ¼ lb patty) = 50% fat reduction 3/12/2012 37

MC & HPMC FILM FRMATIN 3/12/2012 38

Surface Activity - 1% Gum Solutions Chemistry Surface Tension (Dynes/cm) Water 72 Xanthan 69 CMC 68 Na Alginate 62 PG Alginate 58 MC 53-59 HPMC 45-55 Chemistry MC HPMC Surface Activity Least Most N. Sakar CRI Report #823965, 1982 39

MC & HPMC Film Formation Benefits Improved adhesion of coatings Reduced oil pick up (also a function of thermal gelation) Increased hold time under heat lamp Reduced runoff in oven Reduced browning 3/12/2012 40

MC & HPMC Film Formation MC & HPMC are very surface active 3/12/2012 41

MC & HPMC Film Formation Tri-colored/tri-flavored film for a coating, as an insert between layers, encapsulation, etc 3/12/2012 42

MC & HPMC Film Formation - Glazes Dry mix glaze on chicken breast (applied as a powder to the moist cold chicken) with METHCEL and without METHCEL 3/12/2012 43

MC & HPMC FAM STABILITY 3/12/2012 44

Surface Activity of MC & HPMC MC & HPMC stabilize emulsions, foams and dispersions by both decreasing the surface tension and increasing the viscosity Hydrophobic Hydrophilic il Water MC/HPMC il High Shear Storage Water No MC/HPMC Emulsion Foam Dispersion With MC/HPMC il-in-water Air-in-water Solids-in-water 45

MC & HPMC Foam Stability Eggless Meringue 3/12/2012 46

MC & HPMC Foam Stability Control (Egg) METHCEL F50 FG 3/12/2012 47

MC & HPMC Moisture Control 3/12/2012 48

MC & HPMC Moisture Migration Control MC & HPMC reabsorb moisture when food cools after heating and retains moisture during shelf storage. Cold moisture migration in chilled and frozen storage (ice crystal control) Where cold moisture migration control might be used? o o o o Baked goods (reduce staling) Frozen doughs and batters (Cookie, Brownie, Rolls & Bread) Frozen Cakes and Muffins Fillings on dough based substrates 3/12/2012 49

Moisture Control and Retention with MC & HPMC 3/12/2012 50

MC & HPMC Use of Multiple Properties 3/12/2012 51

MC & HPMC Using Multiple Properties Gluten Replacement Gel Strength Weaker Gel to ensure the bread can rise Medium Viscosity Needs to be able to thicken dough Too thick Will not raise during proving or baking & difficult to work with HPMC Surface Activity Enhances and stabilizes air pocket structure in dough Gelation Temp Higher Gelation Temp (70-90 0 C) to gel later during the baking process 52

MC & HPMC Using Multiple Properties In Reformed Potato Products: Make mash formable in the cold (viscosity control) Maintain shape when fried and re-cooled (thermal gelation & viscosity) Dramatically reduce bursting leading to improved yields and better safety (thermal gelation, moisture management) Make mash slippery reducing starch damage during extrusion Reduce oil uptake (thermal gelation, film formation) 3/12/2012

MC & HPMC Using Multiple Properties In Predusts: o o o Increases Batter Pick-up (Viscosity) Manages moisture migration (thermal gelation, film formation) Prevents batter blow-offs (thermal gelation, film formation) In Batters: o o o Reduced fat uptake (thermal gelation, film formation) Increases hold time (thermal gelation, film formation) Preserves crispiness in oven reconstituted products (film formation) 3/12/2012 54

MC & HPMC How to Incorporate MC & HPMC in Food Systems 3/12/2012 55

MC & HPMC - Incorporation Methods Dry Blending (flour, sugar,salt, spices, etc.) 7:1 Dispersant/MC or HPMC Food ils (soy, corn, canola, cottonseed) 5:1-8:1 il/mc or HPMC ther Liquids (corn syrup, HFCS, glycerin) Hot Processing Steps Direct Cold Water 3/12/2012 56

MC & HPMC Delayed Hydration Technique Add MC or HPMC to hot system - MC or HPMC won t hydrate in hot conditions - Product (dips/soups/etc) will stay thin during hot HTST or UHT; thicken upon cooling Improves pumpability of hot filled products Better efficiency of heat transfer during processing lower processing time Less burn on 57

MC Starch Synergy Methylcellulose has a synergistic effect when used in combination with modified waxy maize starches Reduce MC and starch levels save on cost Fewer calories Increased hot cling Greater hot viscosity Less starchy mouthfeel in sauces 58

Sodium Carboxymethylcellulose (CMC) 3/12/2012 60

CMC Common Applications Gluten-free and conventional breads Pancakes, wraps, tortillas Cakes and cookies: Dough and dry mixes Bakery creams, fruit preparations Glazes, coatings and toppings of bakery products Dairy products Soups, sauces, dressings, marinades Beverages and Wine Meat Products 3/12/2012 61

CMC - Advantages Broad viscosity range from very low to extremely high o 30 60,000 cps (2 %, Brookfield) Always available in high quality (not depending on harvesting) High degree of purity (> 99.5 %) Conformity of all standards for food and pharmaceutical applications Narrow specifications for all relevant product parameters Prepared from wood pulp GM free 62

CMC - Advantages Absolutely odorless and tasteless (e.g. Guar smells like beans) Absolutely clear and transparent solutions in water (unique in the world hydrocolloids) CMC & HPMC Guar Gum Agar 63

CMC Key Properties Soluble in Cold and Hot Water Thickener Increased Plasticity and Elasticity (improved machinability) Freeze Thaw Stability High Water Binding Emlulsifier Protein protection Compatible With ther Hydrocolloids 3/12/2012 64

CMC The Chemistry - Na + - Na + H H H H H H H H - Na + - Na + 3/12/2012 65

CMC - Production CMC products are tailor made Main product characteristics are controlled by: degree of polymerisation (DP) CMC degree of substitution DS particle size H H - N a + H - N a + - N a + H H H H H - N a + Sodium Carboxymethylcellulose (CMC) 66

CMC - Degree of Polymerization (DP) DP = (Average Chain Length) Is controlled by the manufacturing process raw material (cellulose) source Determines the viscosity development of the CMC Range includes grades from low to extremely high viscosity 67

CMC - Degree of substitution (DS) DS Average Number of CM-groups per Glucose Unit Impact of increasing DS Higher gloss 0.7 Smoother flow behavior, less pseudoplastic Clearer solutions (no fibers) Higher stability in low water content products Higher salt tolerance 0.9 68

CMC - Particle Sizes Powdered Grades Will Clump if attempt to put directly into solution Requires dry blending agent Granular Grades Goes into solution without clumping Takes longer to hydrate Instantized Grades Very good dispersibility in cold water Fast viscosity build up No lumping 3/12/2012 69

CMC Effect of Concentration o Effect of Heat o o Effect of Shear o o Viscosity build is not linear (doubling will increase viscosity 6-10X) With increasing temperature the viscosity of the CMC solution decreases (reversible) At temperatures above 90C (194 F) all CMC grades are thin flowing. The higher the shear, the greater the thinning effect. Reverses and builds back viscosity after shear is removed Effect of Salt Concentration o Effect of ph Viscosity decreases as salt concentration increases o Maximum viscosity between ph 6.5-8.5 o Viscosity falls on each side of that range 70

Viscosity [mpa s] CMC - Viscosity Relation: CMC concentration and viscosity 20000 18000 16000 14000 12000 10000 8000 6000 4000 2000 CRT 30 CRT 100 CRT 1000 CRT 2000 CRT 10000 CRT 20000 CRT 30000 CRT 40000 CRT 50000 0 0 1 2 3 4 5 6 7 8 Concentration [%] 71 in water, 15 C, BF LVT

CMC - Heat Impact The viscosity decreases during heating process. Reversible Process viscosity increase again by decreasing the temperature! 14.000 12.00 0 10.000 8.000 6.000 4.000 2.000 0 example: WALCEL CRT 10000 GA 20 30 50 70 100 Temperature [ºC] 72

Viscosity / mpa s CMC - Impact of Shear Aqueous CMC-Solutions, Concentration 1.0 % by weight 100000 10000 CRT 60.000 PPA 07 1000 CRT 20000 PA 07 CRT 2.000 PA CRT 1000 GA 07 100 10 0,01 0,1 1 10 100 1000 10000 Shear rate / s-1 73

CMC - Salt Tolerance General behavior in the presence of salts: Tolerance is limited Viscosity decreases with increasing salt levels Higher DS CMCs are more stable than lower 1. CMC 2. Salt The moment of salt (e.g. table salt) addition is important Dissolved CMC is more stable against salts than CMC which is integrated in salt water The viscosity development of CMC is suppressed due to salt water 74

Viscosity [mpa s] CMC - Effect of ph on Viscosity 6000 Maximum viscosity between ph 6.5-8.5 Insoluble at ph < 3 (free acid form) Strong viscosity decrease at ph < 6 Viscosity in relation to ph value (CMC atro) Slight viscosity drop at ph > 9 5000 4000 3000 2000 1000 CRT 30, V2 CRT 100, V2 CRT 1000, V2 CRT 2000, V2 CRT 10000, V1 CRT 20000 (07), V1 CRT 30000, V1 CRT 40000, V1 CRT 60000 (07), V0.5 0 0 2 4 6 8 10 12 14 ph value 75

CMC Synergistic Combinations of CMC With ther Hydrocolloids 76 3/12/2012 76

Viscosity [mpas] CMC + Guar Viscosity increase Synergism CMC - Guar without shear stress Walocel CRT 60000 PA 07 - Guar 5000, concentration: 0.5 % in sum 2000 1750 1500 1250 1000 750 500 250 0 0.5 % (atro), measured value Theoretical value 0 10 20 30 40 50 60 70 80 90 100 Amount CMC in the blend [%] 77 3/12/2012 77

CMC + Locust Bean Gum Improved stability and functionality Synergism of blends (50 : 50) Improved heat resistance compared to pure CMC Increased cold functionality compared to pure LBG Viscosity win (10 % at low shear) Good shear stability 78 3/12/2012 78

CMC + Gelforming Hydrocolloids Improved stability and functionality "Synergism" between CMC and classic gelformers such as κ-carrageenan, Agar, Starch ) Improved gel quality Prolonged stability No / less syneresis Increased elasticity 79 3/12/2012 79

CMC - verview on Food Applications Foods Containing CMC 80 3/12/2012 80

CMC - Functions in Food Thickener, Viscosifier (e.g. beverages, soups, dressings, sauces) Gives viscosity to aqueous solutions Texturizer (e.g. beverages, fruitpreparation) Improves body and mouthfeel, keeps consistency stable over storage time Improve elasticity and plasticity (e.g. extruded products, bakery products) Good machinability / simplified post-processing 81 3/12/2012 81

CMC - Functions in Food Crystallisation control (e.g. ice cream, frozen dough products) Slows down the crystallisation speed, reduced crystal growth/size Delayed retrogradation of amylose (anti staling agent) Waterbinding (e.g. meat products, bakery products) Prevents water loss, suppressed syneresis Prolonged freshness Mouthfeel enhancer (e.g. fat-reduced products like fresh cheese preparations, soups, sauces, beverages) Simulates a fatty mouth feel, improved creaminess 82 3/12/2012 82

CMC - Functions in Food Protein protection (e.g. fresh cheese, acidified dairy drinks) CMC protects proteins against the effects of acid and heat Stabilizer (e.g. soups, dressings, sauces) Keeps molecules stable and suspends particles Emulsifier (e.g. spreadable cheese, dressings) Stabilizes hydrophilic and lipophilic components, support of classic emulsifiers 83 3/12/2012 83

CMC - Functions in Food Gelling support (e.g. fresh cheese preps, desserts) CMC improves the quality of gels and supports gel-forming hydrocolloids Foam stabilization Fixing of foams, constant density, prolonged stand-up Partial replacement of traditional additives Fat and oil Proteins (Proteins from milk/whey, meat, soy, wheat) Sugar and lactose 84 3/12/2012 84

Guar Replacement with CMC Guar Gum Guar provides thickening, texturizing, moisture-binding and freeze-thaw stability 70-80% of guar gum is being used oilfield applications Gum gum supply short of demand by ~25% in 2012 Current prices roughly $7/lb 1% viscosity = 3500 5000 cps CMC is a suitable, cost effective replacement 40,000 or 50,000 viscosity grade 1:1 replacement Synergy: 20/80 & 35/65 Guar/CMC offers a 2x viscosity gain vs expected value 85

Guar Replacement with CMC Properties Guar gum Cellulose gum Cold and hot water soluble Dissolution time Medium - Fast Fast Solution Transparency Cloudy Clear Flavor Beany Neutral Viscosity range 5000-7000 @1% 30 to 50,000 @ 2% Viscosity w/shear Shear Thinning Shear Thinning Viscosity w/heat Heat Thinning Heat Thinning Synergy Xanthan Guar, MC ph Stability 5 7, loss below 3.5 Loss below 3.2 Moisture Holding Good Good Freeze Thaw Stability Ionic Non Ionic Ionic Milk Interaction Not Known Protective 86

CMC - Incorporation Methods Procedure Physical Form Recommended Preparation Granular Type (GA) Powder Type (PA) Fine Powder Type (PPA) Separate Solution + High speed mixer should be used and CMC grades should be added slowly to aqueous solution. The dissolution time is about 30 60 minutes. Dry Blend Mixture + + Premix CMC grades with other powder ingredients of the formulation to avoid agglomeration or lumps. Dispersion in organic solvents or oil + + + CMC grades are dispersed in organic solvents/oil. The CMC dispersion is than added to water while stirring 3/12/2012 87

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